Herbicidal N-haloacetyl-2-alkyl-6-acylanilines

ABSTRACT

Compounds of the formula ##STR1## wherein R 1  is alkyl or alkoxy; R 2  is substituted alkyl or substituted alkenyl containing 1 or 2 hydroxy or alkoxy substituents, acyl, and ketal group of the formula ##STR2## wherein n=2, 3 or 4, R 4  is alkyl and R 5  is hydrogen or alkyl, an oxime of the formula ##STR3## wherein R 6  is hydrogen or alkyl; R 3  is hydrogen or alkyl; X is halo and Y is oxygen or sulfur have herbicidal activity.

This is a division of application Ser. No. 53,877, filed July 2, 1979,now U.S. Pat. No. 4,244,730.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,141,989 discloses3-(N-chloroacetyl(-N-2,6-dialkylphenylamino)-gammabutyrolactones) asfungicides.

U.S. Pat. No. 4,055,410 discloses substituted bromo and chloroacetamidesas herbicides.

SUMMARY OF THE INVENTION

This invention relates to novel N-haloacetyl-2-alkyl-6-acylanilinecompounds, methods of their use as herbicides and herbicidalcompositions thereof. It has now been found that the placement ofcertain acyl, ketal, oxime, hydroxyalkyl and alkoxyalkyl substituents onthe 6-position of N-haloacetyl-2-alkyl anilines results in compoundshaving herbicidal activity. The compounds of the invention areparticularly effective for pre-emergent treatment of grassy weeds.

DESCRIPTION OF THE INVENTION

The compounds of the invention are represented by the formula: ##STR4##wherein R¹ is alkyl of 1 to 4 carbon atoms; or alkoxy of 1 to 4 carbonatoms;

R² is substituted alkyl of 1 to 6 carbon atoms or substituted alkenyl of1 to 6 carbon atoms substituted with 1 or 2 hydroxy groups or 1 or 2alkoxy groups of 1 to 3 carbon atoms; acyl of 2 to 4 carbon atoms; agroup of the formula ##STR5## wherein n=2, 3 or 4; R⁴ is alkyl of 1 to 3carbon atoms and R⁵ is hydrogen or alkyl of 1 to 3 carbon atoms; a groupof the formula ##STR6## wherein R⁴ is defined above and R⁶ is hydrogenor alkyl of 1 to 3 carbon atoms

R³ is hydrogen or alkyl of 1 to 4 carbon atoms; X is halogen; and Y isoxygen or sulfur.

Representative R¹ groups are methyl, ethyl, n-propyl, i-propyl, methoxy,ethoxy and i-propoxy. Preferably R¹ is methyl.

Representative substituted alkyl and acyl R² groups are 1-hydroxyethyl,1,2-bis-methoxyethyl, acetyl and propionyl.

Representative ketal R² groups are ##STR7##

Representative oxime R² groups are ##STR8##

Representative R³ groups are hydrogen, methyl, ethyl, i-propyl,n-propyl, n-butyl, i-butyl. ##STR9##

Representative X groups are chloro, bromo, fluoro, iodo. Preferably X ischloro. Preferably Y is oxygen.

The compounds of the invention may be made according to the followingscheme. ##STR10##

The above reactions are conventional deacetylation (1), acetylation (2and 5), ketalization (3a and 3c) and reduction (3b) reactions and may beperformed by known procedures. Reaction (4) is generally conducted byreacting substantially equimolar amounts of the carbonyl compound (II)and the alkoxyamine in the liquid phase in an inert diluent at atemperature of 0° to 100° C. Generally, the alkoxyamine is generated insitu from the corresponding alkoxyamino hydrochloride or methoxyaminehydrochloride, and a base, e.g., an inorganic alkali metal carbonatesuch as potassium carbonate or a trialkyl amine such as triethylamine.

The compounds of the present invention are, in general, herbicidal inboth pre- and post-emergent applications, but are particularly effectivein pre-emergent applications. For pre-emergent control of undesirablevegetation, the herbicidal compounds will be applied in herbicidallyeffective amounts to the locus or growth medium of the vegetation, e.g.soil infested with seeds and/or seedlings of such vegetation. Suchapplication will inhibit the growth of or kill the seeds, germinatingseeds and seedlings. For post-emergent applications, the herbicidalcompounds will be applied directly to the foliage and other plant parts.Generally, the herbicidal compounds of the invention are effectiveagainst weed grasses as well as broad-leaved weeds. Some may beselective with respect to the type of application and/or type of weed.The compounds of the invention are particularly effective aspre-emergent herbicides against weed grasses.

The compounds, when applied to growing plants above the ground in suchan amount that the compounds will not kill beneficial plants, also showefficient plant growth regulating or retarding effects and may beadvantageously employed, for example, to prevent or retard the growth oflateral buds in plants and to promote the thinning out of superfluousfruits in various fruit trees.

The compounds can be applied in any of a variety of compositions. Ingeneral, the compounds can be extended with a carrier material of thekind used and commonly referred to in the art such as inert solids,water and organic liquids.

The compounds will be included in such compositions in sufficient amountso that they can exert an herbicidal or growth-regulating effect.Usually from about 0.5 to 95% by weight of the compounds are included insuch formulations.

Solid compositions can be made with inert powders. The compositions thuscan be homogeneous powders that can be used as such, diluted with inertsolids to form dusts, or suspended in a suitable liquid medium for sprayapplication. The powders usually comprise the active ingredient admixedwith minor amounts of conditioning agent. Natural clays, eitherabsorptive, such as attapulgite, or relatively non-absorptive, such aschina clays, diatomaceous earth, synthetic fine silica, calcium silicateand other inert solid carriers of the kind conventionally employed inpowdered herbicidal compositions can be used. The active ingredientusually makes up from 0.5-90% of these powder compositions. The solidsordinarily should be very finely divided. For conversion of the powdersto dusts, talc, pyrophyllite, and the like, are customarily used.

Liquid compositions including the active compounds described above canbe prepared by admixing the compound with a suitable liquid diluentmedium. Typical of the liquid media commonly employed are methanol,benezene, toluene, and the like. The active ingredient usually makes upfrom about 0.5 to 50% of these liquid compositions. Some of thesecompositions are designated to be used as such, and others to beextended with large quantities of water.

Compositions in the form of wettable powders or liquids can also includeone or more surface-active agents, such as wetting, dispersing oremulsifying agents. The surface-active agents cause the compositions ofwettable powders or liquids to disperse or emulsify easily in water togive aqueous sprays.

The surface-active agents employed can be of the anionic, cationic ornonionic type. They include, or example, sodium long-chain carboxylates,alkyl aryl sulfonates, sodium lauryl sulfate, polyethylene oxides,lignin sulfonates and other surface-active agents.

When used as a pre-emergent treatment, it is desirable to include afertilizer, an insecticide, a fungicide or another herbicide.

The amount of compound or composition administered will vary with theparticular plant part or plant growth medium which is to be contacted,the general location of application--i.e., sheltered areas such asgreenhouses, as compared to exposed areas such as fields--as well as thedesired type of control. Generally for both pre- and post-emergentherbicidal control, the compounds of the invention are applied at ratesof 0.2 to 60 kg/ha, and the preferred rate is in the range 0.5 to 40kg/ha. For plant growth regulating or retarding activity, it isessential to apply the oxime compounds at a concentration not so high asto kill the plants. Therefore, the application rates for plant growthregulating or retarding activity will generally be lower than the ratesused for killing the plants. Generally, such rates vary from 0.1 to 5kg/ha, and preferably from 0.1 to 3 kg/ha.

Herbicidal tests on representative compounds of the invention were madeusing the following methods.

Pre-Emergent Herbicidal Test

An acetone solution of the test compound was prepared by mixing 375 mgof the compound, 118 mg of a nonionic surfactant and 18 ml of acetone.10 ml of this solution was added to 40 ml of water to give the testsolution.

Seeds of the test vegetation were planted in a pot of soil and the testsolution was sprayed uniformly onto the soil surface at a dose of 27.5micrograms/cm². The pot was watered and placed in a greenhouse. The potwas watered intermittently and observed for seedling emergence, healthof emerging seedlings, etc., for a 3-week period. At the end of thisperiod, the herbicidal effectiveness of the compound was rated based onthe physiological observations. A 0-to-100 scale was used, 0representing no phytotoxicity, 100 representing complete kill. Theresults of these tests appear in Table I.

Post-Emergent Herbicidal Test

The test compound was formulated in the same manner as described abovefor the pre-emergent test. This formulation was uniformly sprayed on 2similar pots of 24-day-old plants (approximately 15 to 25 plants perpot) at a dose of 27.5 microgram/cm². After the plants had dried, theywere placed in a greenhouse and then watered intermittently at theirbases, as needed. The plants were observed periodically for phytotoxiceffects and physiological and morphological responses to the treatment.After 3 weeks, the herbicidal effectiveness of the compound was ratedbased on these observations. A 0-to-100 scale was used, 0 representingno phytotoxicity and 100 representing complete kill. The results ofthese tests appear in Table I.

EXAMPLE 1 Preparation of N-Chloroacetyl-2-methyl-6-acetylaniline

A. N-Acetyl-2-methyl-6-acetylaniline (76.1 g) in water (300 ml), ethanol(300 ml), concentrated hydrochloric acid (300 ml) and concentratedsulfuric acid (15 ml) were refluxed for 24 hours. The solution wascooled and concentrated ammonium hydroxide was added to pH 10. Thesolution was extracted with dichloromethane. The extracts were dried(MgSO₄) and stripped. 2-methyl-6-acetylaniline (49.3 g) was obtained asa tan solid.

B. 2-Methyl-6-acetylaniline (25 g) and pyridine (26.5 g) in 1 litermethylene chloride were cooled in an ice-acetone bath. A solution ofchloroacetyl chloride (37.9 g) in 100 ml methylene chloride was drippedin slowly. The solution was stirred at room temperature for 2 hours,washed with 10% HCl, 10% NaOH, dried (MgSO₄) and stripped. Yield: thetitle product as a white solid, MP 88°-89° C.

EXAMPLE 2 Preparation of2,4,5-Trimethyl-2-(3-methyl-2-chloroacetamidophenyl) dioxolane

The product from Example 1 (10.6 g), 2,3-dihydroxybutane (8.5 g) andp-toluene sulfonic acid (1.5 g) in 200 ml benzene were refluxed to 2hours, removing water with a Dean-Stark trap. The solution wash washedwith 10% NaOH, dried (MgSO₄) and stripped. The product waschromatographed on a silica gel column, eluting with 30% ether-hexane.Yield: 3.8 g of the title product, mp 55°-57° C.

EXAMPLE 3 Preparation of (3'-methyl-2'-chloroacetamido) acetophenoneO-methyloxime

2-Methyl-6-acetylaniline (from Example 1A) was refluxed withmethoxyamine hydrochloride in ethanol to yield (3'-methyl-2'-amino)acetophenone O-methyl oxime (I).

Compound I (1.72 g) and 1 g triethylamine in 35 ml methylene chloridewere cooled in an ice bath and 1.1 g chloroacetyl chloride was addedslowly.

The solution was stirred at room temperature overnight, washed with 10%HCl, 10% NaHCO₃, water and dried (MgSO₄). The solvent was stripped toyield 1.2 g of the title product, m.p. 119°-120° C.

                                      TABLE A                                     __________________________________________________________________________    Compounds of the Formula                                                       ##STR11##                                                                                                 analysis                                                                 m.p. C      H      N                                  No.                                                                              R.sup.1                                                                             R.sup.3                                                                            R.sup.2   °C.                                                                         CAL.                                                                              FD.                                                                              CAL.                                                                              FD.                                                                              CAL.                                                                              FD.                            __________________________________________________________________________    1  CH.sub.3                                                                            H                                                                                 ##STR12##  oil  13.1.sup.a                                                                        11.7.sup.a                                   2  C.sub.2 H.sub.5                                                                     H                                                                                 ##STR13##  87-91                                                                              59.25                                                                             53.39                                                                            6.40                                                                              6.37                                                                             4.94                                                                              5.01                           3  C.sub.2 H.sub.5                                                                     H                                                                                 ##STR14##  oil  60.50                                                                             58.76                                                                            6.77                                                                              6.37                                                                             4.70                                                                              5.01                           4  CH(CH.sub.3).sub.2                                                                  H                                                                                 ##STR15##  97-98                                                                              60.50                                                                             55.1                                                                             6.77                                                                              5.89                                                                             4.70                                                                              4.34                           5  CH.sub.3                                                                            H                                                                                 ##STR16##  86-87                                                                              13.2.sup.a                                                                        16.1.sup.a                                   6  CH.sub.3                                                                            H                                                                                 ##STR17##  55-57                                                                              60.50                                                                             58.94                                                                            6.77                                                                              6.63                                                                             4.70                                                                              4.58                           7  CH(CH.sub.3).sub.2                                                                  H                                                                                 ##STR18##  67-68                                                                              62.66                                                                             63.44                                                                            7.42                                                                              7.53                                                                             4.30                                                                              4.4                            8  C.sub.2 H.sub.5                                                                     H                                                                                 ##STR19##  72-74                                                                              61.62                                                                             62.51                                                                            7.11                                                                              7.24                                                                             4.49                                                                              4.48                           9  CH.sub.3                                                                            H                                                                                 ##STR20##  oil  57.45                                                                             59.92                                                                            6.68                                                                              6.47                                                                             5.16                                                                              5.27                           10 CH.sub.3                                                                            H                                                                                 ##STR21##  119-120                                                                            56.58                                                                             56.85                                                                            5.94                                                                              6.16                                                                             11.0                                                                              11.24                          11 CH(CH.sub.3).sub.2                                                                  H                                                                                 ##STR22##  108-110                                                                            59.46                                                                             60.62                                                                            6.77                                                                              6.82                                                                             9.91                                                                              9.53                           12 CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR23##  61-64                                                                              60.09                                                                             59.21                                                                            7.40                                                                              7.33                                                                             4.67                                                                              4.48                           13 CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR24##  oil  62.80                                                                             61.44                                                                            6.78                                                                              6.96                                                                             5.23                                                                              4.87                           14 CH.sub.3                                                                            H                                                                                 ##STR25##  75-77                                                                              60.13                                                                             59.76                                                                            5.89                                                                              6.05                                                                             5.84                                                                              5.69                           15 CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR26##  oil  61.53                                                                             59.07                                                                            6.36                                                                              6.08                                                                             5.52                                                                              5.12                           16 CH.sub.3                                                                            H                                                                                 ##STR27##  77-79                                                                              58.02                                                                             55.7                                                                             6.20                                                                              6.14                                                                             6.15                                                                              6.0                            17 C.sub.2 H.sub.5                                                                     H                                                                                 ##STR28##  113-114                                                                            59.62                                                                             58.89                                                                            6.67                                                                              6.75                                                                             5.80                                                                              6.0                            18 CH.sub.3                                                                            H                                                                                 ##STR29##  88-89                                                                              58.54                                                                             54.53                                                                            5.36                                                                              4.95                                                                             6.21                                                                              5.7                            19 CH(CH.sub.3).sub.2                                                                  H                                                                                 ##STR30##  118-120                                                                            61.53                                                                             56.71                                                                            6.36                                                                              5.59                                                                             5.52                                                                              4.29                           __________________________________________________________________________     .sup.a Chlorine                                                          

                  TABLE I                                                         ______________________________________                                        HERBICIDAL ACTIVITY                                                           Pre/Post % Control                                                            No.   L       M        P     C      W     O                                   ______________________________________                                        1     65/60   60/60    75/20  97/60 100/60                                                                              99/15                               2     55/0    55/0     60/0  100/20 100/45                                                                              98/20                               3     0/0     0/0      0/0   90/0   90/0  55/0                                4     0/0     0/0      0/0   90/0   90/0  50/0                                5     10/0    0/0      0/0   95/0   100/0 70/0                                6     50/0    78/0     95/0  100/65 100/85                                                                              98/20                               7     0/0     30/0     0/0   92/0   95/30 90/10                               8     45/0    82/0     85/0  100/55 100/85                                                                              95/20                               9     0/0     0/0      0/0   100/0  90/0  15/0                                10    40 30/0 60/0     95/0  100/60 15/0                                      11    0/0     0/0      0/0   90/0   95/0  0/0                                 12    0/30    0/20     0/25  95/15  97/15 30/0                                13    0/15    0/10     0/0   90/40  95/50 40/20                               14    10/55   10/45    25/65 100/50 100/50                                                                              97/15                               15    0/0     0/0      0/0   97/55  95/30 25/0                                16    0/0     0/0      0/0   75/0   80/0  0/0                                 17    0/0     0/0      0/0   90/0   95/0  15/0                                18    0/0     0/0      0/0   98/0   95/0  0/0                                 19    0/0     0/0      0/0   80/0   85/0  20/0                                ______________________________________                                         L = Lambsquarter (Chenopodium album)                                          M = Mustard (Brassica arvensis)                                               P = Pigweed (Amaranthus retroflexus)                                          C = Crabgrass (Digitaria sanguinalis)                                         W = Watergrass (Echinochola crusgalli)                                        O = Wild Oats (Avenua fatua)                                             

What is claimed is:
 1. A compound of the formula: ##STR31## wherein R¹is alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; R² isacyl of 2 to 4 carbon atoms or a group having the formula: ##STR32##wherein R⁴ is alkyl of 1 to 3 carbon atoms and R⁶ is hydrogen or alkylof 1 to 3 carbon atoms; R³ is hydrogen or alkyl of 1 to 4 carbon atoms;and X is halogen.
 2. A compound according to claim 1 wherein R² is##STR33##
 3. A compound according to claim 2 wherein R¹ is methyl, R³ ishydrogen, X is chloro, and R⁴ and R⁶ are methyl.
 4. An herbicidalcomposition comprising a biologically inert carrier and an herbicidallyeffective amount of the compound of the formula defined in claim
 1. 5. Amethod for killing vegetation which comprises applying to saidvegetation or its growth environment an herbicidally effective amount ofthe compound of the formula defined in claim 1.